EP1632542B1 - Oberflächenbehandlungsmittel mit fluorpolymer - Google Patents

Oberflächenbehandlungsmittel mit fluorpolymer Download PDF

Info

Publication number
EP1632542B1
EP1632542B1 EP20040729759 EP04729759A EP1632542B1 EP 1632542 B1 EP1632542 B1 EP 1632542B1 EP 20040729759 EP20040729759 EP 20040729759 EP 04729759 A EP04729759 A EP 04729759A EP 1632542 B1 EP1632542 B1 EP 1632542B1
Authority
EP
European Patent Office
Prior art keywords
monomer
agent
fluorine
test
repeating units
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP20040729759
Other languages
English (en)
French (fr)
Other versions
EP1632542A1 (de
EP1632542A4 (de
Inventor
Ikuo c/o DAIKIN INDUSTRIES LTD. YAMAMOTO
Tetsuya c/o DAIKIN INDUSTRIES LTD. MASUTANI
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Daikin Industries Ltd
Original Assignee
Daikin Industries Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Daikin Industries Ltd filed Critical Daikin Industries Ltd
Publication of EP1632542A1 publication Critical patent/EP1632542A1/de
Publication of EP1632542A4 publication Critical patent/EP1632542A4/de
Application granted granted Critical
Publication of EP1632542B1 publication Critical patent/EP1632542B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/18—Materials not provided for elsewhere for application to surfaces to minimize adherence of ice, mist or water thereto; Thawing or antifreeze materials for application to surfaces
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/22—Esters containing halogen
    • C08F220/24—Esters containing halogen containing perhaloalkyl radicals
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
    • D06M15/277—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof containing fluorine
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/10—Repellency against liquids
    • D06M2200/11—Oleophobic properties
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/10—Repellency against liquids
    • D06M2200/12—Hydrophobic properties
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/23907—Pile or nap type surface or component
    • Y10T428/23986—With coating, impregnation, or bond
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer

Definitions

  • the present invention relates to a polymer and a treatment which impart excellent water repellency, oil repellency and soil resistance to a textile, a masonry, an electrostatic filter, a dust protective mask, and a part of fuel cell.
  • a fluorine-containing acrylate polymer is used as an active component of a water-and oil-repellent agent.
  • Side chain fluoroalkyl groups in practically used fluorine-containing acrylate monomers usually have at least 8 carbon atoms.
  • the fluorine-containing acrylate monomer is excessively hydrophobic since the length of the fluoroalkyl chain is long. The excessive hydrophobicity has caused various problems on the preparation and properties of the fluorine-containing acrylate polymer.
  • JP-A-63-90588 , JP-A-63-99285 and JP-A-01-315471 disclose that a fluorine-containing acrylate polymer wherein the alpha-position is substituted with fluorine, chlorine or the like has good properties such as good adhesion to a substrate, high strength of a film and good water- and oil-repellency.
  • These publications describe that the fluoroalkyl group used in Examples has at least 8 carbon atoms and does not suggest to use the acrylate monomer having the fluoroalkyl group having at most 6 carbon atoms.
  • Another object of the present invention is to provide a substitute compound having chemical skeleton structure which is different from the above-mentioned "telomer”.
  • the present invention provides a surface treatment agent comprising a fluorine-containing polymer comprising:
  • the fluorine-containing polymer constituting the surface treatment agent of the present invention is a copolymer comprising
  • the repeating units (A) are derived from (a) the fluorine-containing monomer of the formula (I).
  • the Rf group is preferably a perfluoroalkyl group.
  • the carbon number of the Rf group is from 1 to 6, for example, from 1 to 4.
  • Y is preferably an aliphatic group having 1 to 10 carbon atoms, an aromatic group or cycloaliphatic group having 6 to 10 carbon atoms, a -CH 2 CH 2 N(R 1 ) SO 2 - group (R 1 is an alkyl group having 1 to 4 carbon atoms) or a - CH 2 CH(OY 1 )CH 2 - group (Y 1 is a hydrogen atom or an acetyl group).
  • the aliphatic group is preferably an alkylene group (particularly the carbon number is from 1 to 4, for example, 1 or 2).
  • the aromatic group and cycloaliphatic group may be substituted or unsubstituted.
  • the repeating units (B) are derived from (b) the monomer free from a fluorine atom.
  • the monomer (b) is preferably a fluorine-free monomer having a carbon-carbon double bond.
  • the monomer (b) is preferably a vinyl monomer which is free from fluorine.
  • the fluorine atom-free monomer (b) is generally a compound having one carbon-carbon double bond.
  • fluorine atom-free monomer (b) examples include, for example, ethylene, vinyl acetate, vinylidene halide, acrylonitrile, styrene, polyethyleneglycol (meth) acrylate, polypropyleneglycol (meth)acrylate, methoxypolyethyleneglycol (meth)acrylate, methoxypolypropyleneglycol (meth) acrylate, vinyl alkyl ether and isoprene.
  • the fluorine atom-free monomer (b) is not limited to these examples.
  • the repeating units (C) are derived from the crosslinkable monomer (c).
  • the crosslinkable monomer (c) may be a fluorine-free monomer having at least two reactive groups and/or carbon-carbon double bonds.
  • the crosslinkable monomer (c) may be a compound having at least two carbon-carbon double bonds, or a compound having at least one carbon-carbon double bond and at least one reactive group. Examples of the reactive group include a hydroxyl group, an epoxy group, a chloromethyl group, a blocked isocyanate group, an amino group and a carboxyl group.
  • crosslinkable monomer (c) examples include diacetoneacrylamide, (meth)acrylamide, N-methylolacrylamide, hydroxymethyl (meth)acrylate, hydroxyethyl (meth)acrylate, 3-chloro-2-hydroxypropyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, N,N-diethylaminoethyl (meth)acrylate, butadiene, chloroprene and glycidyl (meth)acrylate, to which the crosslinkable monomer is not limited.
  • the amount of the fluorine atom-free monomer (b) may be from 0.1 to 100 parts by weight, for example, from 0.1 to 50 parts by weight, and the amount of the crosslinkable monomer (c) may be at most 50 parts by weight, for example, at most 20 parts by weight, particularly, from 0.1 to 15 parts by weight, based on 100 parts by weight of the fluorine-containing monomer (a).
  • a method of dissolving the monomer(s) into an organic solvent in the presence of a polymerization initiator replacing the atmosphere by nitrogen, and stirring the mixture with heating at the temperature within the range from 30°C to 120°C for 1 hour to 10 hours.
  • the polymerization initiator include azobisisobutyronitrile, benzoyl peroxide, di-tert-butyl peroxide, lauryl peroxide, cumene hydroperoxide, t-butyl peroxypivalate and diisopropyl peroxydicarbonate.
  • the polymerization initiator may be used in the amount within the range from 0.01 to 20 parts by weight, for example, from 0.01 to 10 parts by weight, based on 100 parts by weight of total of the monomers.
  • the organic solvent is inert to the monomer(s) and dissolves the monomer(s), and examples thereof include acetone, chloroform, HCHC225, isopropyl alcohol, pentane, hexane, heptane, octane, cyclohexane, benzene, toluene, xylene, petroleum ether, tetrahydrofuran, 1,4-dioxane, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, 1,1,2,2-tetrachloroethane, 1,1,1-trichloroethane, trichloroethylene, perchloroethylene, tetrachlorodifluoroethane and trichlorotrifluoroethane.
  • the organic solvent may be used in the amount within the range from 50 to 2,000 parts by weight, for example, from 50 to 1,000
  • an emulsion polymerization there can be used a method of emulsifying monomers in water in the presence of a polymerization initiator and an emulsifying agent, replacing the atmosphere by nitrogen, and polymerizing with stirring, for example, at the temperature within the range from 50°C to 80°C for 1 hour to 10 hours.
  • polymerization initiator for example, water-soluble initiators (e.g., benzoyl peroxide, lauroyl peroxide, t-butyl perbenzoate, 1-hydroxycyclohexyl hydroperoxide, 3-carboxypropionyl peroxide, acetyl peroxide, azobisisobutylamidine dihydrochloride, azobisisobutyronitrile, sodium peroxide, potassium persulfate and ammonium persulfate) and oil-soluble initiators (e.g., azobisisobutyronitrile, benzoyl peroxide, di-tert-butyl peroxide, lauryl peroxide, cumene hydroperoxide, t-butyl peroxypivalate and diisopropyl peroxydicarbonate) are used.
  • the polymerization initiator may be used in the amount within the range from 0.01 to 10 parts by weight based on 100 parts by weight of the monomers.
  • the monomers are atomized in water by using an emulsifying device capable of applying a strong shattering energy (e.g., a high-pressure homogenizer and an ultrasonic homogenizer) and then polymerized with using the oil-soluble polymerization initiator.
  • an emulsifying device capable of applying a strong shattering energy (e.g., a high-pressure homogenizer and an ultrasonic homogenizer) and then polymerized with using the oil-soluble polymerization initiator.
  • a strong shattering energy e.g., a high-pressure homogenizer and an ultrasonic homogenizer
  • various emulsifying agents such as an anionic emulsifying agent, a cationic emulsifying agent and a nonionic emulsifying agent can be used in the amount within the range from 0.5 to 20 parts by weight based on 100 parts by weight of the monomers.
  • a compatibilizing agent e.g., a water-soluble organic solvent and a low-molecular weight monomer
  • a compatibilizing agent capable of sufficiently compatibilizing them is preferably added to these monomers.
  • water-soluble organic solvent examples include acetone, methyl ethyl ketone, ethyl acetate, propylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol, tripropylene glycol and ethanol.
  • the water-soluble organic solvent may be used in the amount within the range from 1 to 50 parts by weight, e.g., from 10 to 40 parts by weight, based on 100 parts by weight of water.
  • the low-molecular weight monomer examples include methyl methacrylate, glycidyl methacrylate and 2,2,2-trifluoroethyl methacrylate.
  • the low-molecular weight monomer may be used in the amount within the range from 1 to 50 parts by weight, e.g., from 10 to 40 parts by weight, based on 100 parts by weight of total of monomers.
  • the surface treatment agent of the present invention is preferably in the form of a solution, an emulsion or an aerosol.
  • the surface treatment agent generally comprises the fluorine-containing polymer and a medium (particularly a liquid medium, for example, an organic solvent and/or water).
  • the concentration of the fluorine-containing polymer in the surface treatment agent may be, for example, from 0.1 to 50 % by weight.
  • the surface treatment agent can be applied to a substrate to be treated by a know procedure.
  • the surface treatment agent is diluted or dispersed with an organic solvent or water, is adhered to surfaces of the substrate by a well-known procedure such as an immersion coating, a spray coating and a foam coating, and is dried. If necessary, the surface treatment agent is applied together with a suitable crosslinking agent, followed by curing.
  • a suitable crosslinking agent for example, a water repellent agent and an oil repellent agent
  • mothproofing agents for example, a water repellent agent and an oil repellent agent
  • softeners for example, antimicrobial agents, flame retardants, antistatic agents, paint fixing agents, crease-proofing agents, etc.
  • the concentration of the fluorine-containing compound in the treatment liquid contacted with the substrate may be from 0.05 to 10% by weight, based on the treatment liquid.
  • the concentration of the fluorine-containing compound in the treatment liquid may be from 0.1 to 5% by weight, based on the treatment liquid.
  • a stain blocker may be used. When the stain blocker is used, it is preferable to use an anionic emulsifier or a nonionic surfactant.
  • the substrate to be treated with the surface treatment agent (for example, a water- and oil-repellent agent) of the present invention include a textile, masonry, a filter (for example, an electrostatic filter), a dust protective mask, a part of fuel cell (for example, a gaseous diffusion electrode and a gaseous diffusion support), glass, paper, wood, leather, fur, asbestos, brick, cement, metal and oxide, ceramics, plastics, a coated surface and a plaster.
  • the textile may be particularly a carpet.
  • the textile has various examples.
  • the textile examples include animal- or vegetable-origin natural fibers such as cotton, hemp, wool and silk; synthetic fibers such as polyamide, polyester, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride and polypropylene; semi-synthetic fibers such as rayon and acetate; inorganic fibers such as glass fiber, carbon fiber and asbestos fiber; and a mixture of these fibers.
  • the treatment agent of the present invention is excellent in resistance in a detergent liquid and brushing (mechanical), it can be suitably used for carpet made from nylon or polypropylene.
  • the textile may be in any form such as a fiber, a fabric and the like.
  • the carpet When the carpet is treated with the surface treatment agent of the present invention, the carpet may be formed after treating fibers or yarns with the surface treatment agent, or the formed carpet may be treated with the surface treatment agent.
  • a treated fabric is stored in a thermo-hygrostat having a temperature of 21°C and a humidity of 65% for at least 4 hours.
  • a test liquid (isopropyl alcohol (IPA), water, and a mixture thereof, as shown in Table 2) which has been also stored at 21°C is used.
  • the test is conducted in an air-conditioned room having a temperature of 21°C and a humidity of 65%.
  • a droplet of the test liquid in an amount of 0.05 mL is softly dropped by a micropipette on the fabric. If the droplet remains on the fabric after standing for 30 seconds, the test liquid passes the test.
  • the water-repellency is expressed by a point corresponding to a maximum content (% by volume) of isopropyl alcohol (IPA) in the test liquid which passes the test.
  • the water-repellency is evaluated as twelve levels which are Fail, 0, 1, 2, 3, 4, 5, 6, 7, 8, 9 and 10 in order of a poor level to an excellent level.
  • Table 2 Water-repellency test liquid Point (% by volume) Isopropyl alcohol Water 10 100 0 9 90 10 8 80 20 7 70 30 6 60 40 5 50 50 4 40 60 3 30 70 2 20 80 1 10 90 0 0 100 Fail Inferior to isopropyl alcohol 0/water 100
  • a treated fabric is stored in a thermo-hygrostat having a temperature of 21°C and a humidity of 65% for at least 4 hours.
  • a test liquid (shown in Table 3) which has been also stored at 21°C is used. The test is conducted in an air-conditioned room having a temperature of 21°C and a humidity of 65%.
  • a droplet of the test liquid in an amount of 0.05 mL is softly dropped by a micropipette on the fabric. If the droplet remains on the fabric after standing for 30 seconds, the test liquid passes the test.
  • the oil-repellency is expressed by a maximum point of the test liquid which passes the test.
  • Test liquids (3 mass % in ethyl acetate) are prepared from polymers obtained in Preparative Examples and Comparative Preparative Examples. After the test liquid is left standing for 24 hours at room temperature (25°C), the evolution of sedimentation of the treatment liquid is observed. Good: No sedimentation Fair: Slight sedimentation Poor: Much sedimentation
  • the reaction was monitored by a gas chromatography, and the disappearance of monomer peaks was confirmed and regarded as the completion of the reaction.
  • methanol was added to a solution containing a polymer to precipitate a yellow precipitation.
  • the precipitation was filtered under a reduced pressure and dried in a vacuum desiccator to give a cream-colored flake solid (10.59g) (Polymer yield: 70.60%).
  • the polymer was identified by an elemental analysis (Table 4), 1 H-NMR, 19 F-NMR and 13 C-NMR.
  • the reaction was monitored by a gas chromatography, and the disappearance of peaks of the 9F-Alc/ ⁇ Cl monomer and the stearyl acrylate monomer was confirmed and regarded as the completion of the reaction.
  • methanol was added to a solution containing a polymer to precipitate a white precipitation.
  • the precipitation was filtered under a reduced pressure and dried in a vacuum desiccator to give a white powder compound (7.86 g) (Polymer yield: 78.6%).
  • the polymer was identified by an elemental analysis (Table 4), 1 H-NMR, 19 F-NMR and 13 C-NMR. The composition of monomers in the polymer was almost the same as the charged monomers.
  • the polymer (6 g) obtained in Comp. Preparative Example 3 was dissolved in HCFC225 (600 g). After three nylon test fabrics (510 mm ⁇ 205 mm) were immersed in this test solution (150 g) for about 5 minutes, and the solvent was removed by centrifugal dehydrator (500 rpm, 20 seconds). The same procedure was conducted for three PET test fabrics (510 mm ⁇ 205 mm), three PET/cotton mixture test fabrics (510 mm ⁇ 205 mm) and three cotton test fabrics (510 mm ⁇ 205 mm). Then each test fabric was dried at 28°C for one night.
  • each one fabric from nylon test fabrics, PET test fabrics, PET/cotton mixture test fabrics and cotton test fabrics was treated by a pin tenter at 80°C for 3 minutes, and each fabric was cut into halves (255 mm ⁇ 205 mm). One half was used for a shower water repellency test, and the other half was used for a water repellency test and an oil repellency test.
  • each one fabric from nylon test fabrics, PET test fabrics, PET/cotton mixture test fabrics and cotton test fabrics was treated by a pin tenter at 150°C for 3 minutes, and each fabric was cut into halves (255 mm ⁇ 205 mm). One half was used for a shower water repellency test, and the other half was used for a water repellency test and an oil repellency test.
  • the polymer obtained in Preparative Example 4 was treated as in Example 1, and then subjected to the shower water repellency test, the water repellency test and the oil repellency test.
  • the test results are shown in Table 5.
  • the polymer obtained in Preparative Example 6 was treated as in Example 1, and then subjected to the shower water repellency test, the water repellency test and the oil repellency test.
  • the test results are shown in Table 5.
  • the polymer obtained in Comparative Preparative Example 1 was treated as in Example 1, and then subjected to the shower water repellency test, the water repellency test and the oil repellency test.
  • the test results are shown in Table 5.
  • each of test fabrics was treated by a pin tenter at 150°C for 3 minutes, each fabric was cut into halves (255 mm ⁇ 205 mm). One half was used for a shower water repellency test, and the other half was used for a water repellency test and an oil repellency test.
  • Example 1 Test fabric Treatment shower water Water repellency Oil repellency shower water Water repellency Oil repellency Nylon RT 70 3 2 80 5 6 80°C 50 3 2 80 5 6 150°C 70 7 6 90 9 7 PET RT 50 3 1 70 6 6 80°C 50 4 2 80 6 6 150°C 70 6 3 100 7 6 PET/ Cotton RT 50 5 1 50 7 3 80°C 50 7 1 70 8 4 150°C 70 7 1 80 9 4 Cotton RT 50 9 4 50 7 3 80°C 50 9 4 50 7 4 150°C 50 9 5 50 8 5 Comp.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Textile Engineering (AREA)
  • Combustion & Propulsion (AREA)
  • Materials Engineering (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
  • Paints Or Removers (AREA)

Claims (13)

  1. Mittel, das als ein Oberflächenbehandlungsmittel geeignet ist und ein fluorhaltiges Polymer umfasst, das umfasst:
    (A) von einem Monomer der Formel:
    Figure imgb0010
     abgeleitete Repetiereinheiten, worin
    X Cl, Br, I, CFX1X2 (worin jedes von X1 und X2 H, F oder Cl ist), Cyano, lineares oder verzweigtes C1-20-Fluoroalkyl, optional substituiertes Benzyl oder optional substituiertes Phenyl ist,
    Y eine C1-10-aliphatische Gruppe, eine C6-10-aromatische oder -cycloaliphatische Gruppe, -CH2CH2N(R1)SO2- (worin R1 ist C1-4-Alkyl) oder -CH2CH(OY1)CH2- (worin Y1 ist H oder Acetyl) ist, und
    Rf lineares oder verzweigtes C1-6-Fluoroalkyl ist;
    (B) von einem fluorfreien Monomer abgeleitete Repetiereinheiten, und
    (C) optional Repetiereinheiten, die von einem vernetzbaren Monomer abgeleitet sind.
  2. Mittel nach Anspruch 1, worin Rf in Formel (I) C1-4-Fluoroalkyl ist.
  3. Mittel nach Anspruch 1, worin Rf in Formel (I) Perfluoroalkyl ist.
  4. Mittel nach Anspruch 1, worin die Repetiereinheiten (B) von einem Monomer der Formel

            CH2=CA1COOA2

    abgeleitet sind,
    worin A1 H oder Methyl ist, und A2 eine C1-30-Kohlenwasserstoffgruppe (insbesondere Alkyl wiedergegeben durch CnH2n+1 worin n ist 1-30) ist.
  5. Mittel nach Anspruch 1, worin die Repetiereinheiten (C) von einem fluorfreien Monomer abgeleitet sind, das mindestens zwei reaktive Gruppen und/oder Kohlenstoff-Kohlenstoff Doppelbindungen hat.
  6. Mittel nach Anspruch 1, worin das fluorhaltige Polymer 0.1-50 Gewichtsteile des fluoratom-freien Monomers und ≤ 20 Gewichtsteile des vernetzbaren Monomers pro 100 Gewichtsteile des fluorhaltigen Monomers enthält.
  7. Mittel nach Anspruch 1, das in der Form einer Lösung, einer Emulsion oder eines Aerosols ist.
  8. Mittel nach einem der Ansprüche 1-8, das weiterhin Wasser enthält.
  9. Fluorhaltiges Polymer, umfassend:
    (A) von einem Monomer der Formel:
    Figure imgb0011
     abgeleitete Repetiereinheiten, worin
    X Cl, Br, I, CFX1X2 (worin jedes von X1 und X2 H, F oder Cl ist), Cyano, lineares oder verzweigtes C1-20-Fluoroalkyl, optional substituiertes Benzyl oder optional substituiertes Phenyl ist,
    Y eine C1-10-aliphatische Gruppe, eine C6-10-aromatische oder -cycloaliphatische Gruppe, -CH2CH2N(R1)SO2- (worin R1 C1-4-Alkyl ist) oder -CH2CH(OY1)CH2- (worin Y1 H oder Acetyl ist) ist, und Rf lineares oder verzweigtes C1-6-Fluoroalkyl ist;
    (B) Repetiereinheiten, die von einem fluorfreien Monomer abgeleitet sind, und
    (C) optional Repetiereinheiten, die von einem vernetzbaren Monomer abgeleitet sind.
  10. Verfahren, um einem Substrat wasserabweisende Wirkung, ölabweisende Wirkung und Verschmutzungsbeständigkeit zu verleihen, wobei das Verfahren die Behandlung des Substrats mit dem Mittel nach einem der Ansprüche 1-6 umfasst.
  11. Verfahren nach Anspruch 10, bei dem das Substrat ein Textil, ein Mauerwerk, ein Filter (beispielweise ein elektrostatischer Filter), eine Staubschutzmaske, eine Brennstoffzelle, Glas, Papier, Holz, Leder, Pelz, Asbest, Ziegel, Zement, Metall und Oxid, Keramiken, Kunststoffe, eine beschichtete Oberfläche oder ein Pflaster ist.
  12. Textil, das mit dem Mittel nach einem der Ansprüche 1-6 behandelt worden ist.
  13. Teppich, der mit dem Mittel nach einem der Ansprüche 1-6 behandelt worden ist.
EP20040729759 2003-05-02 2004-04-27 Oberflächenbehandlungsmittel mit fluorpolymer Expired - Lifetime EP1632542B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP2003126992 2003-05-02
JP2004033669A JP4329559B2 (ja) 2003-05-02 2004-02-10 含フッ素重合体を含んでなる表面処理剤
PCT/JP2004/006056 WO2004096939A1 (ja) 2003-05-02 2004-04-27 含フッ素重合体を含んでなる表面処理剤

Publications (3)

Publication Number Publication Date
EP1632542A1 EP1632542A1 (de) 2006-03-08
EP1632542A4 EP1632542A4 (de) 2008-11-19
EP1632542B1 true EP1632542B1 (de) 2014-07-16

Family

ID=33422095

Family Applications (1)

Application Number Title Priority Date Filing Date
EP20040729759 Expired - Lifetime EP1632542B1 (de) 2003-05-02 2004-04-27 Oberflächenbehandlungsmittel mit fluorpolymer

Country Status (11)

Country Link
US (2) US7915337B2 (de)
EP (1) EP1632542B1 (de)
JP (1) JP4329559B2 (de)
KR (1) KR100752462B1 (de)
CN (1) CN100577767C (de)
BR (1) BRPI0409933B1 (de)
CA (1) CA2523029C (de)
MX (1) MXPA05011475A (de)
TW (1) TWI325888B (de)
WO (1) WO2004096939A1 (de)
ZA (1) ZA200507474B (de)

Families Citing this family (47)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5229005B2 (ja) * 2003-05-02 2013-07-03 ダイキン工業株式会社 含フッ素重合体を含んでなる表面処理剤
JP4779374B2 (ja) * 2005-02-10 2011-09-28 ダイキン工業株式会社 含フッ素重合体の製造方法および表面処理
CA2607627C (en) 2005-05-09 2010-12-14 Daikin Industries, Ltd. Fluorosilicones and fluorine- and silicon-containing surface treatment agent
US7754836B2 (en) 2005-09-01 2010-07-13 Daikin Industries, Ltd. Water and oil repellent composition and treatment method
JP4946084B2 (ja) * 2006-02-10 2012-06-06 ダイキン工業株式会社 含フッ素重合体を鞘に含む芯鞘構造複合繊維および該複合繊維を有する物品
JP5200403B2 (ja) * 2006-03-30 2013-06-05 旭硝子株式会社 撥液剤組成物、撥液加工方法、撥液膜を有する物品
CN101415792B (zh) * 2006-03-30 2012-05-30 旭硝子株式会社 防液剂组合物、防液加工方法、具有防液膜的物品
JP2007269642A (ja) * 2006-03-30 2007-10-18 Daikin Ind Ltd フルオロアクリレート重合体を含有する化粧料
JP2007332482A (ja) * 2006-06-14 2007-12-27 Toray Ind Inc 透湿防水加工布帛
US7385077B1 (en) 2007-03-27 2008-06-10 E. I. Du Pont De Nemours And Company Fluoroalkyl surfactants
US20100227173A1 (en) * 2007-05-15 2010-09-09 Daikin Industries, Ltd. Water-repellent oil-repellent antifouling agent having good solubility in solvent
EP2045276A1 (de) * 2007-10-05 2009-04-08 E.I. Du Pont De Nemours And Company Fluorpolymer
JP5439743B2 (ja) 2007-10-11 2014-03-12 ユニマテック株式会社 撥水撥油剤
JP5315663B2 (ja) 2007-10-22 2013-10-16 ユニマテック株式会社 撥水撥油剤
US7829477B2 (en) 2007-10-29 2010-11-09 E.I. Dupont De Nemours And Company Fluorinated water soluble copolymers
US20090148653A1 (en) * 2007-12-07 2009-06-11 E.I. Du Pont De Nemours And Company Fluoropolymer emulsions
WO2009084635A1 (ja) * 2007-12-28 2009-07-09 Daikin Industries, Ltd. 電子部品用の水性コーティング剤
KR101266749B1 (ko) 2008-02-06 2013-05-28 다우 코닝 코포레이션 플루오로실리콘 및 플루오르- 및 규소-함유 표면 처리제
US10077327B2 (en) * 2008-03-28 2018-09-18 Daikin Industries, Ltd. Fluorine-containing copolymer and water- and oil-repellent agent
CN101981070B (zh) * 2008-03-28 2016-04-06 大金工业株式会社 含氟聚合物和防水防油剂
JP5546459B2 (ja) 2008-03-31 2014-07-09 ダイキン工業株式会社 フルオロシリコーン分散液および含フッ素含ケイ素表面処理剤
JP5510319B2 (ja) 2008-06-12 2014-06-04 ユニマテック株式会社 水性エマルジョンの製造方法
US20100003290A1 (en) * 2008-09-28 2010-01-07 Kobo Products, Inc. Oil and water repellent cosmetic powder and methods of making and using same
JP5324255B2 (ja) * 2009-02-25 2013-10-23 特種東海製紙株式会社 シート状物
WO2011021619A1 (ja) * 2009-08-18 2011-02-24 ダイキン工業株式会社 共重合体および紙用処理剤および加工紙
KR101330384B1 (ko) * 2009-09-01 2013-11-15 다이킨 고교 가부시키가이샤 종이용 내수 내유제, 처리 방법 및 처리지
EP2302130A1 (de) 2009-09-26 2011-03-30 Huntsman Textile Effects (Germany) GmbH Zusammensetzung für die Öl- und/oder Wasserabweisende Ausrüstung von Fasermaterialien
US8507601B2 (en) 2009-11-09 2013-08-13 E. I. Du Pont De Nemours And Company Method using fluoropolymer emulsions
EP2499198B1 (de) * 2009-11-09 2013-07-17 E. I. du Pont de Nemours and Company Fluorpolymeremulsionen
US8329822B2 (en) 2009-11-09 2012-12-11 E.I. Du Pont De Nemours And Company Fluoropolymer emulsions
CA2782134C (en) * 2009-12-10 2016-12-13 Invista Technologies S.A.R.L. Soil repellency aqueous dispersions, soil repellant soft articles, and methods of making the same
JP5902397B2 (ja) * 2010-03-30 2016-04-13 ダイキン工業株式会社 結晶性含フッ素アクリル酸エステル重合体、その製法、および撥水撥油剤
JP5626337B2 (ja) * 2010-03-30 2014-11-19 ダイキン工業株式会社 α−クロロアクリレートを使用した撥水撥油剤
JP2011214216A (ja) * 2011-07-22 2011-10-27 Komatsu Seiren Co Ltd 撥水撥油性布帛
JP5574128B2 (ja) * 2012-07-27 2014-08-20 香川県 透湿防水シートの製造方法及び撥水性の向上方法
DE102012020053A1 (de) * 2012-10-12 2014-04-17 Brauns-Heitmann Gmbh & Co. Kg Zubereitung für eine Appretur von Flächengebilden
EP2945994B1 (de) 2013-01-18 2018-07-11 Basf Se Beschichtungszusammensetzungen auf basis von acryldispersionen
EP3015480B1 (de) 2013-06-28 2019-11-06 Daikin Industries, Ltd. Oberflächenbehandlungsmittel
JP2015085232A (ja) * 2013-10-29 2015-05-07 東洋紡株式会社 耐油性エレクトレットろ材
CN103757915A (zh) * 2013-11-01 2014-04-30 巨化集团技术中心 一种皮革用新型环保防水防油剂
WO2015152207A1 (ja) 2014-04-04 2015-10-08 東洋紡株式会社 エレクトレット
JP5725243B2 (ja) * 2014-06-16 2015-05-27 香川県 透湿防水シート
CN105085792B (zh) * 2015-09-17 2018-06-19 安徽森普新型材料发展有限公司 一种有机氟单体改性丙烯酸乳液的制备方法
WO2017057148A1 (ja) 2015-10-02 2017-04-06 東洋紡株式会社 エレクトレットおよびエレクトレットフィルター
BR102017021055A2 (pt) * 2017-09-29 2019-04-16 Ripack Embalagens Ltda. Solução para o tratamento de madeira
CN112218696B (zh) 2018-06-01 2022-12-30 日东电工株式会社 过滤器滤材和具备该过滤器滤材的过滤器单元
CN110128901A (zh) * 2019-05-29 2019-08-16 苏州鹏瑞纳米科技有限公司 一种防水剂及其制备方法

Family Cites Families (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4267653A (en) * 1980-01-16 1981-05-19 Esco Corporation Locking device for excavating equipment
FR2483447A1 (fr) * 1980-06-03 1981-12-04 Ugine Kuhlmann Composition et procede pour la protection des materiaux contre les souillures
US4592930A (en) * 1984-05-11 1986-06-03 The Dow Chemical Company Perfluorocarbon based polymeric coatings having low critical surface tensions
EP0247489B1 (de) * 1986-05-28 1993-08-25 Daikin Industries, Limited Fluor enthaltende, Wasser und Ölabweisende Zubereitung
JPS6390588A (ja) 1986-10-06 1988-04-21 Daikin Ind Ltd 撥水撥油剤
JPS6399285A (ja) * 1986-05-28 1988-04-30 Daikin Ind Ltd 撥水撥油剤
JPH01197570A (ja) * 1988-02-01 1989-08-09 Daikin Ind Ltd 低屈折率ハードコート剤
JP2770387B2 (ja) 1988-03-16 1998-07-02 ダイキン工業株式会社 防汚加工剤
EP0333083A3 (de) 1988-03-16 1990-05-30 Daikin Industries, Limited Wasser, Öl und Schmutz abweisendes Veredlungsmittel
JPH03103409A (ja) 1989-09-16 1991-04-30 Daikin Ind Ltd ポリ（α―フルオロアクリル酸エステル）の製造方法
JPH0778154B2 (ja) * 1991-07-11 1995-08-23 ヘキスト合成株式会社 含フッ素アクリル系共重合体水性エマルジョンの製造方法及びその組成物
JPH0517538U (ja) 1991-08-19 1993-03-05 アルプス電気株式会社 光フアイバ用検出ヘツド
US6037429A (en) * 1995-06-16 2000-03-14 3M Innovative Properties Company Water-soluble fluorochemical polymers for use in water and oil repellent masonry treatments
JP3542201B2 (ja) * 1995-06-29 2004-07-14 三菱レイヨン株式会社 含フッ素重合体
JP3961644B2 (ja) * 1997-10-22 2007-08-22 関西ペイント株式会社 撥水性を有する共重合体水溶液もしくは水分散液、及びその製造方法、及びこれを含む水性塗料組成物
JP2002105433A (ja) * 2000-10-02 2002-04-10 Lion Corp フッ素含有表面処理剤
JP4247657B2 (ja) * 2001-07-30 2009-04-02 Ｄｉｃ株式会社 防汚加工方法、及び該加工方法を施した基材
JP4130947B2 (ja) 2002-07-08 2008-08-13 Ｈｏｙａ株式会社 内視鏡
WO2005097850A1 (ja) * 2004-04-09 2005-10-20 Daikin Industries, Ltd. メーソンリー処理のための重合体および処理剤
JP5017538B2 (ja) 2010-02-18 2012-09-05 株式会社高尾 弾球遊技機

Also Published As

Publication number Publication date
TWI325888B (en) 2010-06-11
KR100752462B1 (ko) 2007-08-24
JP2004352976A (ja) 2004-12-16
WO2004096939A1 (ja) 2004-11-11
CA2523029A1 (en) 2004-11-11
EP1632542A1 (de) 2006-03-08
MXPA05011475A (es) 2006-03-08
ZA200507474B (en) 2006-07-26
TW200502375A (en) 2005-01-16
US7915337B2 (en) 2011-03-29
BRPI0409933B1 (pt) 2015-08-25
US20110135871A1 (en) 2011-06-09
CN1784480A (zh) 2006-06-07
CN100577767C (zh) 2010-01-06
BRPI0409933A (pt) 2006-04-25
EP1632542A4 (de) 2008-11-19
KR20060008955A (ko) 2006-01-27
CA2523029C (en) 2011-02-22
US20060205864A1 (en) 2006-09-14
US9328455B2 (en) 2016-05-03
JP4329559B2 (ja) 2009-09-09

Similar Documents

Publication Publication Date Title
EP1632542B1 (de) Oberflächenbehandlungsmittel mit fluorpolymer
EP1739143B1 (de) Oberflächenbehandlungsmittel, fluorhaltiges monomer und fluorhaltiges polymer
EP1736486B1 (de) Fluorhaltiges monomer, fluorhaltiges polymer und oberflächenbehandlungsmittel
US7776982B2 (en) Silicon-containing fluorochemical surface-treating agent
EP2799458B1 (de) Fluorhaltige zusammensetzung und fluorhaltiges polymer
JP5397520B2 (ja) 含フッ素組成物および表面処理剤
EP2177550A1 (de) Fluorhaltiges alkohol- und schmutzabweisendes faserverarbeitungsmittel
WO2013058335A1 (ja) 含フッ素組成物およびその用途
EP1881015B1 (de) Fluorpolymer mit s-sulfatgruppe und wasser/öl abweisende zusammensetzung, die das polymer enthält
JP5229005B2 (ja) 含フッ素重合体を含んでなる表面処理剤
EP0368338A2 (de) Wasser und Öl abweisende Zusammensetzung

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20051115

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LI LU MC NL PL PT RO SE SI SK TR

DAX Request for extension of the european patent (deleted)
A4 Supplementary search report drawn up and despatched

Effective date: 20081020

17Q First examination report despatched

Effective date: 20110805

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

INTG Intention to grant announced

Effective date: 20131021

INTG Intention to grant announced

Effective date: 20131029

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

INTG Intention to grant announced

Effective date: 20140220

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LI LU MC NL PL PT RO SE SI SK TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 677660

Country of ref document: AT

Kind code of ref document: T

Effective date: 20140815

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602004045465

Country of ref document: DE

Effective date: 20140828

REG Reference to a national code

Ref country code: NL

Ref legal event code: VDEP

Effective date: 20140716

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 677660

Country of ref document: AT

Kind code of ref document: T

Effective date: 20140716

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20141016

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140716

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20141017

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20141117

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140716

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140716

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140716

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140716

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140716

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140716

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602004045465

Country of ref document: DE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140716

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140716

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140716

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140716

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140716

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed

Effective date: 20150417

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140716

Ref country code: LU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20150427

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140716

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20150430

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20150430

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 13

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20150427

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140716

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 14

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO

Effective date: 20040427

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: TR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140716

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 15

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20230309

Year of fee payment: 20

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: IT

Payment date: 20230310

Year of fee payment: 20

Ref country code: GB

Payment date: 20230309

Year of fee payment: 20

P01 Opt-out of the competence of the unified patent court (upc) registered

Effective date: 20230525

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20230228

Year of fee payment: 20

REG Reference to a national code

Ref country code: DE

Ref legal event code: R071

Ref document number: 602004045465

Country of ref document: DE

REG Reference to a national code

Ref country code: GB

Ref legal event code: PE20

Expiry date: 20240426